Pesticidal compositions containing 1-halo-2-aryloxy-vinyl-(2)-phosphates

ABSTRACT

1-Halo-2-aryloxy-vinyl(2)-phosphates are very effective compounds for combating pests, such as insects, nematodes and representatives of the order Acarina as well as plant-pathogenic bacteria and fungi. The new phosphates may be used in the form of pesticidal preparations.

States atem 11 1 Martin et a1. Dec, 3, 1974 1 PESTICIDAL COMPOSITIONS [58] Field of Search 424/210, 212, 214, 215, CONTAINING 424/217, 218 l-HALO-2-ARYLOXY-VINYL-(2) PHOSPHATES [56] References Cited [75] Inventors: Henry Martin; Jozef Drabek, both UNITED STATES PATENTS of Basel, Switzerland 2,861,914 11/1958 Sailmann 260/951 3,632,692 1/1972 Morales 1 424/210 [73 Asslgnee' Basel swltzerland 3,732,343 5/1973 Martin eta1.. 424/210 [22] Filed: Feb. 14, 1973 Primary ExaminerVincent D. Turner [21] Appl' 332470 Attorney, Agent, or FirmHarry Falber; Frederick H.

Related 1.1.8. Application Data Rabin 1 [62] Division of Ser. No. 64,648, Aug. 17, 1970, Pat. No,

3,732,343. 57] ABSTRACT 1-Halo-2-aryloxy-vinyl(2)-phosphates are very effec- [3O] Forelgn Apphanon Priority Data tive compounds for combating pests, such as insects, 181 1969 swftzerland 12553/69 nematodes and representatives of the order Acarina as Sept. 25, 1969 Sw1tzerland 14452/69 well as plam pathogenic bacteria ;and fungi The e h ht b d'thf.f t"d1 52 us. (:1 424/217, 424/210, 424/214, S fis esmay euse m e Ormo pes a prep,

424/212, 424/215, 424/218 51 1111. C1 A0ln 9/36 21 Clams, N0 Drawings PESTTCTDAL (ZOMPOSlTlONS CONTAINING 1-HALO-2-ARYLOXY-V]INYL-(2)-PHOSPHATES This is a division of application Ser. No. 64,648, filed on Aug. 17, 1970, now US. Pat. No. 3,732,343.

This invention relates to phosphoric acid esters having pesticidal properties, and to a process for their preparation.

The present invention provides compounds having the formula in which Hal represents a bromine atom or a chlorine atom, R and R which may be the same or different, each represents an alkyl radical having from 1 to 4 carbon atoms and R represents an aryl radical, especially a phenyl or naphthyl radical, which may be substituted by a halogen atom, an alkyl radical having from 1 to 4 carbon atoms, an alkoxy radical having from 1 to 4 carbon atoms, an alkylthio radical having from 1 to 4 carbon atoms, an alkylsulphinyl or alkylsulphonyl radical having from 1 to 4 carbon atoms, -NO -CF CN, SCN, a -COOalkyl radical, the alkyl moiety of which has from 1 to 4 carbon atoms or a -COalkyl radical, the alkyl moiety of which has from 1 to 4 carbon atoms. The term halogen as used herein encompasses fluorine, chlorine, bromine and iodine.

Preferred compounds are those having the formula I, in which Hal represents a chlorine atom or a bromine atom, R, and R each represents a methyl or ethyl radical and R represents a phenyl group which may be substituted by one or more of the following substituents:

halogen, methyl, ethyl, methoxy, ethoxy, methylmercapto, methylsulphinyl, methylsulphonyl, -NO --CF ,'-CN, SCN, carbethoxy, carbomethoxy, acetyl or propionyl. The compounds which are especially preferred are those in which Hal represents a chlorine atom and R represents a phenyl group substituted by one or more of the following substituents:

clorine, bromine, iodine, --CN NO or -CF and which can additionally also contain a methyl or ethyl group. 7

The phosphoric acid esters of the formula I are, for example, active against insects, nematodes and representatives of the order Acarina, and also against plantpathogenic bacteria and fungi. When used in appropriately greater amounts, they also show herbicidal and defoliating action.

Their main field of use is combatting all stages of development of sucking and biting insects and Acarina, that is to say, of eggs, larvae, pupae, chrysales and adults or imagines.

The sucking insects include .Diptera and Hymenoptera, for example, aphids (Aphidae) such as Myzus persicae, Doralis fabae, Rhopalosiphum padi, Macrosiphum pisi, Macrosiphum solanifolii, Cryptomyzus korschelti, Sappaphis mali, Hyalopterus arundinis and Myzus cerasi, shield lice and woolly lice (Coccina), for example, Aspidiotus hederae, Lecanium hesperidum Pseudococcus maritimus, and varieties of Thrips (Thysanoptera), for example, Hercinothrips femoralis, bugs, for example, Piesma quadrata, Rhondnius prolixus and Triatoma infestans, and cicadas, for example, Euscelis bilobatus or Nephotettix bipunctatus.

Amongstthe biting insects, there should be mentioned Lepidoptera and Coleoptera, for example Plutella maculipennis, Lymantria dispar, Euproctis chrysorrhoea, Malocosoma neustria, Mamrestra brassicae, Agrotis segetum, Pieris brassicae and Prodenia litura, Ephestia kuhniella, and Galleria mellonella, as well as storage pests, for example, Dermestes frischii, Trogoderma granarius, Tribolium castaneum, Calandra and Sitophilus Zea mais, Stegobium paniceum, Tenebrio molitor, Oryzaephilus surinamensis, Blattel'a german'ica, Periplaneta americana, Blatta orientalis, Blaberus gigantus, Blaberus fuscus, Gryllus domesticus, Sitophilus granarius and Leptinotarsa decemlineata; varieties which inhabit the soil, for example, Agriotes sp. and Melolontha melontha; and termites, for example, Leucotermes sp. or Leucotermes flavipes.

A substantial number of pests is to be found under the order Acarina, for example mites and amongst these especially spider mites (Tetranychidae) for example Tetranychus lelarius, T. althaeae, T. urticae, 'Paratetranychus pilosus and Panonychus ulmi, and gall mites (Eriophyes ribis) and Tarsonemidae, for example,

Hemitarsomenus latus or Tassonemus pallidus.

The order Acarina however also includes the ticks, that is to say, ectoparasites such as Boophilus microplus, Dermanyssus gallinae, Ornithonyssus bacoti, Ornithonyssus sylviarum, Rhipicephalus bursa, Penumonys sus caninum, Laelaps nutalli, Acarapis woodi and Psorergates ovis.

This summary of pests does not in any way claim to be complete. Fundamentally, the phosphates of the formula l have a powerful action against insects and Acarina which are known as pests in crop plant cultures.

Thus, say, the rice stem borer Chillo suppressalis is completely destroyed by 0.02 percent of the compounds of the present invention.

Apart from the insecticidal and acaricidal action, the

one phosphoric acid ester of theformula 0 was? ll lg RIO-IIO OR3 in which Hal, R R and R have the meanings specified above, together with a suitable carrier, for example, a solvent, diluent, dispersing agent, emulsifier, adhesive, thickener, or binder and, if desired other pesticides, for example, insecticides,'acaricides, nematocides, bactericides and fungicides. i

The active ingredients can be used in the most diverse manner, for example, in the form of sprays, concentrates, dusting powders, scattering agents, granules, fly plates or impregnated strips.

In order to manufacture directly sprayable solutions of the compounds of the formula (I) it is for example possible to use mineral oil fractions of high to medium boiling range, such as diesel oil or kerosene, coal tar oil and oil of vegetable or animal origin, as well as hydrocarbons, for example alkylated naphthalenes or tetrahydronaphthalene, optionally using xylene mixtures, cyclohexanols, ketones and also chlorinated hydrocarbons, such as trichlorethane, trichlorethylene or trichlorobenzenes and tetrachlorobenzenes. Advang ageously, organic solvents of boiling point above 100C are used.

Aqueous application forms are particularly appropriately prepared from emulsion concentrates, pastes or wettable spraying powders by adding water. Possible emulsifiers or dispersing agents are non-ionic products, for example condensation products of aliphatic alcohols, amines or carboxylic acids, having a long-chain hydrocarbon radical of about to carbon atoms, with ethylene oxide, for example the condensation product of octadecyl alcohol and to mols of ethylene oxide, or that of technical oleylamine and 15 mols of ethylene oxide or that of dodecylmercaptan and 12 mols of ethylene oxide. As anionic emulsifiers there may be mentioned: the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecyl benzenesulphonic acid, the potassium or triethanolamine salt of oleic acid or of abietic acid or of mixtures of these acids, or the sodium salt of a petroleumsulphonic acid. Possible cationic dispersing agents are quaternary ammonium compounds, such as cetylpyridinium bromide, or dihydroxyethylbenzyldodecylammonium chloride.

Talc, kaolin, bentonite, calcium carbonate and calcium phosphate, but also charcoal, cork powder, wood flour'and other materials of vegetable origin, can be employed for the manufacture of dusting agents and sprinkling agents.

Granules can be manufactured very simply by dissolving an active substance of formula (I) in an organic solvent and applying the solution thus obtained to a granular mineral, for example attapulgite, SiO granicalcium, bentonite and the like, and then again evaporating the organic solvent.

Polymer granules can also be used. They can be manufactured by mixing the active substances of formula I with polymerisable compounds (urea/formaldehyde, dicyandiamide/formaldehyde, melamine/formaldehyde or others), after which a polymerisation is carried out under mild conditions, which leaves the active substances unaffected, with the granulation being carried out whilst the gel formation is still proceeding. It is more advantageous to impregnate finished porous polymer granules (urea/formaldehyde, polyacrylonitn'le, polyesters or others) having a particular surface and an advantageous predeterminable adsorption/- desorption ratiom with the active substances, for example in the form of their solutions (in a lowboiling solvent) and to remove the solvent. Such polymer granules can, in the form of micro-granules of bulk densities of preferably 300 g/litre to 600 g/litre, also be applied with the aid of atomisers. Atomising can be carried out over large areas of crop plant cultures by means of aircraft.

Of course pesticides, fertilisers, surface-active agents or substances for increasing the specific gravity, such as BaSO can be added to the granules,

Granules are also obtainable by compacting the carrier material with the active substances and additives, and subsequent comminution.

The various use forms can, in the usual manner, be provided with additions of substances which improve the distribution, the adhesion, the rain resistance or the penetrating power; fatty acids, resins, glue, caesin, or alginates may be mentioned as such substances.

In general, the agents contain between 0.01 and 95 per cent by weight of active substance, preferably 0.1 to per cent by weight. In certain special fields of use, for example in the case of applications by aircraft, technically pure active substance can also be employed and sprayed.

To broaden the spectrum of action, the active substances of formula I can be combined with known insecticidal, acaricidal and/or nematocidal active substances, of which the following may for example be mentioned:

PHOSPHORIC ACID DERIVATIVES Bis-0,0-diethylphosphoric acid anhydride (TEPP) 0,0,0,0-Tetrapropyldithiopyrophosphate Dimethyl( 2,2,2-trichloro- 1-hydroxyethyl)phosphonate (TRICI-IRORFON) 1 v I ,2-Dibromo-2,2-dichlorethyldimethylphosphate (NA- LED) 2,2-Dichlorovinyldimethylphosphate (DICI-ILORFOS) I Z-Methoxycarbamyll -methylvinyldimethylphosphate (MEVINPHOS) Dimethyll -methyl-2-(methylcarbamoyl )vinylphosphate cis (MONOCROTOPI-IOS) 3-(Dimethoxyphosphinyloxy)-N-methyl-N-methoxycis-croto namide 3-Dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (DICROTOPHOS) I 2-Chloro-2-diethylcarbamoyll -methylvinyldimethylphosphate (PI-IOSPHAMIDON) I 0,0-Diethyl-O-2-(ethylthio)-ethylthiophosphate (DEMETON) 0,0-diethyl-S-2-(ethylthio)-ethylthiophosphate S-Ethylthioethyl-0,0-dimethyl-dithiophosphate (THI- OMETON) 0,0-Diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) O,O-Diethyl-S-2[(ethylthio)ethyl]dithiophosphate (DISULFOTON) 0,0-Dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETONMETl-IYL) 0,0-Dimethyl-S-( 1,2 -dicarbethoxyethyl)dithiophosphate (MALATHION) (0,0,0,0-Tetraethyl-S,S'-methylene-bis-[dithiophosphate] (ETHION) O-Ethyl-S,S-dipropyldithiophosphate 0,0-Dimethyl-S-(N-methyl-N- fonnylcarbamoylmethyl)-dithiophosphate (FORMO- TION) 0,0-Dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate (DIMETHAT) 0,0-Dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate (ETHOATMETHYL) 9 6,7,8,9, l 0, l -l-lexachloro-l ,5 ,5o1,6,9,9a-hexahydro- 6,9-methano-2,3,4 benzo[e]-dioxa-thiepene-3-oxide [Endosulfan] Chlorinated camphor [Toxaphen] Decachloroctahydro-l ,3,4-metheno-2H-cyclobuta[e d] pentalen 2-one DodecachloroctahydrO l ,3 ,4-methenol H- cyclobuta[c d]penta1ene [Mirex] Ethyl-l la,3,3a,4,5,5a,5 6-decachloroctahydro-2- hydroxyl ,3 ,4-methenol H-cyc1obuta[c d]pentalene- 2- laevulinate Bis(pentachloro-2,4-cyclopentadien-1-yl) Dinoctone-o 1,1 l -Trichloro2,2-bis(p-chlorophenyl)ether [DDT] Dichlorodiphenyl-dichlorethane [TDE] Di(p-chlorophenyl)trichloromethylcarbinol [Dicofol] Ethyl-4,4-diechlorophenylglycollate [Chlorobenzylate] Ethyl-4 ,4 '-dibromobenzylate [Bromobenzylate] lsopropyl-4,4'-dichlorobenzylate l ,1 ,1-Tirchloro-2,2bis-(p-methoxyphenyl)ethane [Methoxychlor] Diethyl-diphenyl-dichlorethane Decachloropentacyclo(3,3,2,0 4-one [Chlordecon].

Nitrophenols and Derivatives Various Substances Sabadilla Rotenon Cevadin Veratridin Ryania Pyrethrin 3-Allyl-2-methyl-4-oxo-2-cyclopentenl -ylchrysanthemumate (Allethrin) 6-Chloropiperonyl-chrysanthemumate (Barthrin) 2,4-Dimethylbenzyl-chrysanthemumate (Dimethrin) 2,3,4,5-Tetrahydrophthalimidomethylchrysanthemumate (-Benzyl-3-furyl)-methyl-2,2-dimethyl-3-(2- methylpropyanyl)-cylcopropanecarboxylate Nicotine Bacillus thuringiensis Berliner Dicyclohexylcarbodiimide Diphenyldiimide [azobenzene (sic)] 4-Chlorobenzyl-4-chlorophenylsulphide [Chlorbensid] Creosote oil 6-Methyl-2-oxo-1,3-dithiol o-[4,5- [Quinomethionat] (I)-3-(Z-Furfuryl)-2-methyl-4-oxocyclopent-2-enyl(I)- (cis+trans)chrysanthemum-monocarboxylate [Furethrin] 2-Pivaloyl-indanel ,3-dione [Pindon] 2-Fluorethyl(4-bisphenyl)acetate b]-quinoxaline ill) 2-Fluror-N-methyl-N( l-naphthyl)-acetamicle Pentachlorophenol and salts 2,2,2-Trichloro-N-(pentachlorophenyl)-acetimidoyl chloride I N'-(4-Chloro-2-methylphenyl)-N,N-dimethylformamidine (Chlorphenamidine) 4-Chlorobenzyl-4-fluorophenyl-suilphide (Fluorobeneside) 5 ,6-Dichlorol -phenoxycar'boanyl-2-trifluoromethylbenzimidazole (Fenozaflor) Tricyclohexyl-tin hydroxide 2-Thiocyanatoethyl-lauric acid ester ,B-Butoxy-B'-thiocyanatodiethyl-ether Isobornyl-thiocyanatoacetate p-Chlorophenyl-p-chlorobenzenesulphonate (Ovex) 2,4-Dichlorophenyl-benzenesulphonate p-Chlorophenyl-benzenesulphonate (Fenson) p-Chlorophenyl-2,4,5-trichlorophenylsulphone radifon) p-Chlorophenyl-2,4,S-trichlorophenylsulphide (Tetrasul) Methyl bromide p-Chlorophenyl-phenylsulphone p-Chlorobenzyl-p-chlorophenylsulphide side) 4-Chlorophenyl-2,4,5-trichlorophenylazosulphide 2 p-tert. -Butylphenoxyl -methyl-2-chlorethylsulphite (Tet- (Chloroben- 2(p-tert.-Butylphenoxy) sulphite 4,4'-Dichloro-N-methylbenzenesulphonanilide N-( Z-Fluoro- 1 ,1 ,2,2,-tetrachlorethylthio)- methanesulphonanilide 2-Thiol ,3-dithiolo.(4,5-6)quinoxaline (Thioquinox) Chloromethyl-p-chlorophenylsu]phone (lauseto (sic!) new) l ,3 ,6,8-Tetranitrocarbazole and Prop-2-ynyl-(4-t-butylphenoxy)-cycloliexylsulphite (propargil). I

The action of the phosphoric acid esters of the formula l according to the present invention, can be increased by synergistic agents. Suitable substances for this purpose are, for example, Sesamine, Sesamex, piperonyl cyclonene, piperonyl butoxide, pipe'ronal bis [2-( 2-butoxyethoxy )ethyl] acetate, sulphoxides, propyl isome, N-(Z-ethylhexyl)-5-norbornene-2,3- dicarboxamide, octachlorodipropyl-ether, 2-nitrophenylpropargyl-ether, 4-chlor-2-nitrophenylpropargyl-ether, and 2,4,5-trichlorophenyl-propargylether.

The present invention also provides a process for the manufacture of the phosphoric acid esters of the formula l, which comprises reacting a dihalogenacetic acid ester of the formula namcn cook in which Hal represents a chlorine atom or a bromine atom and R has the meaning specified above, with a trialkylphosphite of the formula cyclohexyl-Z-propinylin which R, and R have the meansings specified above and R represents an alkyl radical having from 1 to 4 carbon atoms. The reaction can be carried out in a so]- vent, for example, toluene, xylene, petrol ether or dioxane, depending upon the speed or sluggishness of the particular reaction.

This reaction is surprising, since it is expressly stated in the literature (F. W. Lichtenthaler, Chem.Rev. 61, 6l2[1961]), in elaboration of the Perkow reaction,

. that the reaction of triethylphosphite with dichloracetic acid ethyl ester only yields undefined end products together with C H Ci. Dichloracetic acid esters, so it is said, are not suitable for the Perkow reaction.

The following Examples illustrate the invention.

EXAMPLE 1 0,0-diethyl-1-(4-chlorophenoxy)-2-chloro-vinylphosphate (Active substance No. 1)

47.6 g of dichloracetic acid 4-chlorophenyl ester were dissolved in 100 ml of toluene. 40 g of triethylphosphite were added to this solution, after which the reaction mixture was warmed to 110cand kept at this temperature for 16 hours.

The toluene was subsequently distilled off and the crude product was purified by means of a molecular distillation apparatus.

Yield 35.3 g; boiling point: 100C/0.003-0.004 mm Hg Analysis for C I-1 0 Calculated Found %P 9.1 8.9 %Cl 20.8 21.3

The structure of the product was confirmed by means of infrared analysis. On addition of SO Cl in CH Cl C1 and added to the double bond. The resulting yellowish trichlorethyl phosphate shows the following analytical figurs for C, H Cl.,O P:

Calculated Found %P 7.52 7.7 %Cl 34.42 34.9

The following phosphoric acid esters can be obtained in asimilar manner: l v

Active I p substance BOIlll'lg point] number R1=Rz Hal R mm.Hg

(i ()il; Ci 135 (lb/0.001

- -N02 (molecular distillation).

C] it 7 7 on; or 135 070.001 N02 (molecular distillation). Cl

8 C9115 Cl 135 C./0.001

Cl (molecular I distillation). on

El 0:115 01 135 O./0.001

-01; (molecular I distillation). Cl

10 C2115 Cl 140 C./0.001

- -N02 (molecular I distillation).

11 C2115 Cl 130 C./0.001

NO2 (molecular I distillation). Cl

12 02115 Cl (J./0.003 (molecular distillation).

13 C2ii5 Ci Q 124-132 C./0.06.

14 C211 Cl Q 125 O./0.008. l Cl 15 C2115 Cl C./0.02.

16.....TIQL. can C1 145 c./0.03.'

17 0211 01 Cl 136 C./0.001

(molecular distillation) Cl 18 C2115 ()1 Cl Melting point:

1!) C211 Cl 123 C./0.001.

20 our. 01 I 070.003 Br (molecular distillation).

21. C211 Ci 132137 C./0.()22.

lit

22 C211 Cl 115-113 C./0.008.

23 C211 Cl Cannot be SCH3 distilled.

Active substance Boiling point/ 0. R1=Rg llal R mm. Hg

5). H CBr Boiling pointom ll ll 145-149 o. (Czl'I5O)2POC-O Cl (molecular I distillation) C Ha n w r 7 V Cannot be 1 ll ll distilled. (C2H50)2P0C0 NO2 6l 0 I-ICBr v Boiling pOllllu.02

' ll ll 133 0.

(C II O) POCO Cl (molecular distillation). l Cl 62- O HCBr Boiling pOllltMlfll II II 128 0. (C H5O)ZPOCO Cl (molecular v a distillation).

63 0 HC-Br Boiling pointum 14 143 C. (CgH50)zP-O-C-O- (molecular I distillation).

64-. O HCBr Boiling point II II (CQH5O)QPOC-O (molecular distillation).

6a. CH3 Boiling pointo-m 'O llC-Br l 151 C.

(molecular (C2HsO)2POC-O -Cl distillation).

l I (ll C113 66. (3 Ha Boiling point O lI()-Br h 148-14J C. (molecular (CzlI5O) POCO Cl distillation).

. or 7 F711 o HCCl Boiling pointnm II II 1 129 0. (iso)C3I-I1OPOC0 'Cl (molecular l distillation). OCI'IJ es. 0 HCCl Boiling pointi II II 129 o. (150) CSIIIOP'COO -Cl (molecular distillation). OCH:

it EXAMPLE 2 a. Dusting agents Equal parts of an active substance according to the invention and of precipitated silica are finely ground. Dusting agents preferably containing l-6 percent of active substance can be manufactured therefrom by mixing with kaolin or talc.

b. Spraying powders I In order to manufacture a spraying powder, the following components are for example mixed and finely ground:

parts of active substance according to the present invention 20 parts of Hisil (highly adsorbent silica) 25 parts of Bolus alba (kaolin) 3.5 parts of a reaction product of p-tert.octylphenol and ethylene oxide and 1.5 parts of sodium l-benyl-2-stearyl-benzimidazole- 6,3 -disulphonate.

c. Emulsion concentrate Easily soluble active substances can also be formulated as an emulsion concentrate according to the following instruction:

20 parts parts of xylene and 10 parts of a mixture of the reaction product of an alkyl phenol with ethylene oxide and calcium dodecylbenzene sulphonate are mixed. On dilution with water to the desired concentration, a sprayable emulsion is produced.

d. Granules a. 7.5 g of one of the active substances of formula I are dissolved in ml of acetone and the acetone solution thus obtained is added to 92 g of granular attapulgite (mesh size: 24/48 meshes- /inch). The whole is well mixed and the solvent is stripped off in a rotary evaporator. Granules containing 7.5 percent of active substance are obtained.

b. In order to manufacture 10 percent strength polymer granules, 1050 to 1100 g of technical active substance of formula I are dissolved in 2 litres of trichlorethylene and sprayed in a fluidised bed granulator, at 1.5 atmospheres gauge spraying pressure, onto 9,230 g of initially introduced porous urea/HCHO-granules. The solvent can again be removed by heating the fluidising air to approx. 50C.

c. In order to manufacture 7.5 percent strength weighted granules, 770 g of a solid technical active substance of formula I, 500 g of BaSO 1000 g of urea and 7730 g of pulverulent, porous polyacrylonitrile' are pressed on a roll mill and subsequently crushed to the desired particle size.

EXAMPLE 3 Active substance No. 1

Concentration Musca domestica Ceratitis [ppm] capitata I000 100 100 100 100 100 10 lOO 100 5 50 100 2.5 50 I00 I25 I 0 50 EXAMPLE 4 Action against Spodoptera littoralis larvae 5 larvae at a time, in the L-2 stage, are placed on a leaf of Malva silvestris which originates from a plant dipped into an aqueouos solution of an active substance, and which had subsequently been introduced into a covered Petri dish. The atmospheric moisturein the dish is maintained with a moistened pad of cottonwood. In this contact test and ingestion test the action was examined after 1 day and after 2 days. If complete destruction has already occurred after 1 day for a particular concentration, a fresh leaf of the same plant is infested with a new population. In this way a possible EXAMPLE 7 ageing of the active substances coating is also taken Action against A his fabae into account in the assessment. p

Young Vicia faba plants approx 6 cm high were in- For active substance No. 25, the following destruction percentages were found: fested with parts of plants attached by Alphls fabae.

After 5 days the starting conditions for the active subconcemmnon [ppm] l day 2 days stance test were present, as a result of the further Egg :88 :88 growth of the plants and approximately strong multipli- 200 100 100 cation of the aphids. The attacked plants were sprayed 28. %gg g? with the emulsions of active substance No. from all 25 80 so sides (contact action), or only from above in the direction of the shoot axis (penetration action). In the latter EXAMPLE 5 case, the experimental animals sitting on the undersides The test with Epilachna Varivastis, the Mexican of the leaves were not struck by the spray jet. If 100 bean bug, was Carried out as follows; Seedlings percent destruction had already occurred after 2 days, of Phaseolus vulgaria in the primary leaf stage, the Ph were re"h1fe$tedgrown in a flow t, were di d i t emulsions Active substance No. 25' achieved the following perof the experimental preparations and subsequently ages o destruction afte 2 and 5 days: allowed to dry. The expermiental animals, L-4 2Q (foncentration Contact action Penetration stage of the beetle, were introduced into a cello- [ppm] 2 days 5 days 2 days phane bag which was subsequently fixed over the 800 m0 m0 100 treated plant by means of a rubber band. After 5 400 [00 0 100 days, the action of the treatment was determined 200 100 I00 by counting the live and deaf animals and by calcu- 5 m0 100 60 lating the percentage destruction.

For active substance No. 43 the following percent- EXAMPLE 8 ages of destruction were found: Action against Spider mites Busch bean plants (Phaseolus vulgaris) in the two- [ppm] 5 days leaf stage were infested with spider mites, 12 hours be- 800 100 fore the treatment with the active aubstances, by plac- 400 ing attacked pieces of leaf from a culture on them, so

200 100 100 100 N that after the end of this time a population in all stages 50 :88 of development was present on the plant. The plants were then sprayed with the emulsified active substance by means ofa chromatography atomiser, until a uni- The test with Orgyia Cohoshgma in t b3 Stage form deposit of droplets was produced on the surface was carried out analogously with young. mallows of the leaf. The results were assessed after 2 and 7 days; (Malva silvestris) as the host plant. 5 larvae were the parts of the plant were inspected under a stereod f h i t. Th lt were 40 microscope in order to calculate the percentages of desessed after 2 and 5'days. If complete destruction h' The h h 0h g was hot Y detectable had already Occurred after 2 days. the plant was after 2 days with this exerimental arrangement, beagain infested. In this way a possible ageing of the Causje the m? development takes 4 days under the active substance coating is also taken into account pamcular m If after 2 days there was 100 in the assessment. I cetnt tiiiStfuCtlOn of larvae and adults, the plant was re- 1n es For acme supstance the following percent' The percentages of destruction of the normally sensiagespf destructlon were achleved: tive variety tetranchus urticae Koch and of the phoscmcemraho" [Plml days 5 days phoric acid ester-tolerant variety Tetranychus telarious :;L, are given in the Table below.

400 100 0 Active substance No. l 7' 200 100 100 a. Action against Tetr. urticae 100 I00 so Destruction EXAMPLE 6 v v I Concentration after 2 days after 7 days Action against Chilo suppressalis (larvae) pp larvae adults eggs larvae adults Act ve substances No. l and 2 were tested forthelr 800 m0 00 80 100 [00 ingestion action against L-2 larvae. For this test, the 188 :88 I88 68 100 100 larvae were placed on the root structure of rice seed- 100 100 O 8 28 lings which had previously been treated by dipping in an emulsion of the active substance. I b, A ti g in t Terr, telarius The evaluation took place after 5 days. Destruction Concentration of the, Mortality in for active substance in active substance concehh'ahoh I am?! 2 5 7 y d I the emulsion No. l and No. 2 [ppm] an'ae a u ts eggs arvae a u ts 800 100 r00 60 100 100 800 PP' 400 100 100 so 100 100 400 pp 100 200 100 100 Y 0 200 pp 100 100 100 80 0 0 so Active substance No. l5 -Continued a. Action against Tetr. urticae Active A B c D E substance DCSUUCUOH No. ppm ppm ppm ppm ppm 5 36 10 10 10 3 0.25 Concentration after 2 days after 7 days 37 50 l 1 L5 000] [ppm] larvae adults eggs larvae adults 3g I 1 15 Q01 2 39 10 10 1.5 0.005 800 100 100 100 100 100 40 10 1 1.5 0.01 400 100 100 100 100 100 41 10 10 10 3 0.025 200 100 100 60 100 100 42 10 1 5 1.5 00002 100 100 100 0 80 100 10 43 10 0.1 0.1 1.5 0.005

. 44 100 0.1 0.1 3 0.25 45 1 0.1 0.1 48 0.1 b. Action agamst Tetr. telar1us 46 1 0.1 0.1 3 0.025 47 100 10 10 3 0.025

Destruct1on 48 10 1 1 6 0.2

49 5 0.1 061 2 0.25 50 100 1 1 48 0.1 Concentration after 2 days after 7 days 51 50 lOO l00 6 0.05 [ppm] larvae adults eggs larvae adults 5 2 50 l l 12 0.01

53 10 0.1 0.1 6 0.1 800 100 100 100 100 100 388 lgg 38 g 188 $8 Minimum conceneration for complete destruction: 10o s0 s0 0 60 100 Active A B c o subgltance [PP l lPP l lPP l [PllPP 0. EXAMPLE 9 54 100 10 50 4 1 Action agamst ectoparasites and vectors 55 10 10 10 4 0.5 56 10 10 10 12 1 T1cks A. Rhipicephalus bursa (adults). The experimental EXAMPLE 1O .anciinlials were brieflfy threated with aqueous :(BMUOH of Action against storage pests when using a 5 percent a 1ut1on series 0 t e active su stance. ssessment Strength dust formulation based on talc after 2 weeks. I I a b. Rhipicephalus bursa (larvae). Method as under A) Assessment after 3 y Varieties of test animal Minimum amount of active substance for l00 des- C. Booph1lus microplus, (larvae). Method as under r m in 24 hours'expg. B). Assessment after 3 days. We (mg of aglwe v substance per m actors Compound No. 37 D. Lucilia sericata (larvae). Chopped horsemeat, mixed with dilution concentrations of an active sub- Gama" coclfmach (Phyllodr0m1a germanica) l2 stance, were admlmstered as food to the larvae of the American cockroach blow-fly. Assessment after 24 hours. lpellplane'a amencana') 50 n Russlan cockroach E. Aedes Ae gyptz (larvae). The larvae of the yellow (Bram ofiqmaiis) 350 fever mosquito were kept 1n a very dilute aqueous solu- 1 s rlmago 50 tion of active substance. Assessment after 24 hours. g ifii "e'gfii"l.lm 5 8 Minimum concentrations for complete destruction: (Dermestes frischii) v larva l2 Active A B j C D E Sitophilus granarius substance F eevil a (larva) N m m m w 0 ppm ppm pp pp pp (Attagenus piceus) 50 House cricket .1 0.1 .003 2 l 8.5 l 1.5 8.001 (Achela domesma) 100 3 10' 10 1 6 0.125 10 50 10 10 6 0.06 13 5 0.1 0.1 1.5 0.01 14 10 1- 0.5 3 0.001 50 EXAMPLE 16 10 0.1 0.1 15 0.012 17 50 1 0.5 3 0.025 Funglcldal Action 1 50 12 0.05 {S 2 01 0.1 3 (mm 1. Rice plants were grown in a greenhouse and 20 10 0.1 0.1 3 8- 3 sprayed once, propylactically, with an aqueous spray- 10(1) 5 ing liquor containing 0.1 percent of the active substances N0. 21. Two days thereafter, the plants were Minimum concentration for m e destruction; treated in this way were infected with conidia of Piricu- I laria 0 zae Bri. and Cav. After 7 da s incubation in a y 3322 A B C D E hum1d1ty chamber, the plants treated with the expen- NQ ppm ppm ppm ppm ppm 60 mental preparation showed a fungal attack of about 10 percent, whilst the untreated control plants were lOO 52 a: 3 percent attacked. 27 10 0.1 0.1 3 006 2. Small agar plates on which Rhizoctonia solani 5g g g 9 g 88: Klihn had grown were covered, in Petri dishes, with 30 l0 l0 5 3 0:025 65 non-sterile soil. An aqueous liquor containing active 31 10 l l 3 I 0.012 substancec No. 38 which was to be tested, was unigi :8 8'; g (H125 formly distributed over the surface of these layers of 35 10 5 3 005 soil. After an incubation time of 48 hours at 24C the growth of the test fungus was examined and assessed. Herein, a test concentration of 100 ppm of active substance showed complete inhibition of fungal growth.

We claim:

1. A pesticidal composition useful for combating pests selected from the group consisting of insects and acarinae comprising (1 a pesticidally effective amount of a compound of the formula in which Hal represents chlorine or bromine; each of R and R represents alkyl of from 1 to 4 carbon atoms; and R represents phenyl, naphthyl or phenyl substituted by from 1 to substituents selected from the group consisting of halogen, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, alkylthio of from 1 to 4 carbon atoms, nitro, trifluoromethyl, cyano, the group COO-alkyl in which the alkyl group has from 1 to 4 carbon atoms and the group CO-alkyl in which the alkyl has from 1 to 4 carbon atoms and (2) a suitable carrier.

2. The composition according to claim 1 in which, in the compound, each of R and R represents methyl or ethyl; and R represents phenyl or phenyl substituted by from 1 to 5 substituents selected from the group consisting of halogen, methyl, ethyl, methoxy, ethoxy, methylmercapto, nitro, trifluoromethyl, carbethoxy, carbomethoxy, acetyl or propionyl.

3. The composition according to claim 2 in which, in the compound Hal represents chlorine; and R represents phenyl substituted by one methyl or ethyl group or by from 1 to 5 substituents selected from the group consisting of chlorine, bromine, iodine, cyano, nitro or trifluoromethyl.

4. A method for combatting pests selected from the group consisting of insects, and acarinae, which comprises applying to said pests a pesticidally effective amount of a compound of the formula in which Hal represents chlorine or bromine; each of R and R represents alkyl of from 1 to 4 carbon atoms; and R represents phenyl, naphthyl or phenyl substituted by from 1 to 5 substituents selected'from the group consisting of halogen, alkyl of from 1 to 4 carbon I by from 1 to 5 substituents selected from the group consisting of halogen, methyl, ethyl, methoxy, ethoxy, ethylmercapto, nitro, trifluoromethyl, carbethoxy, car- 'bomethoxy, acetyl or propionyl.

6. The method according to claim 5 in which, in the compound Hal represents chlorine; and R represents phenyl substituted by one methyl or ethyl group or by from 1 to 5 substituents selected from the group consisting of chlorine, bromine, iodine, cyano, nitro or trifluoromethyl.

7. The method of claim 6 in which the compound is of the formula 0 HC-Cl n n (C2H5O) 2P O C O -Cl 8. The method of claim 6 in which the compound is of the formula (C H O) P O C 0- Cl 9. The method of claim 6 in which the compound is of the formula (C H O) P O (I 0- Cl The method of claim 6 in which the compound is of the formula ac-cl H c o-@-c1 (C2H5O)2P o 11. The method of claim 6 in which the compound is of the formula Y o HC-Cl g s n u (C H O) P O C O--- i/ ---NO 12. The method of claim 6 in which the compound is of the formula 0 HC-Cl 13. The method of claim 6 in which the compound is of the formula o HC-Cl ll ll tc a o) 2P 0 c o- 1 23 24 14. The method of claim 6 in which the compound 18, Th th d f lai 5 in which the compound is of the formula is of the formula HC -c1 HcBr I I 19. The method of claim 5 in which the compound is of the formula 15. The method of claim 6 in which the compound 10 O is of the formula II li (CHO)P OCOOC1 O HC-Cl 2 5 2 It ll H (c d o) P 0 C 0 c1 c 3 (CHIO)III -O(IIIOD --(C H o) 1 -og--o C1-- 20; The method of claim 6 in which the compound cl c 3 is of the formula 16. The method of claim 6 in which the compound 0 BC-Cl is of the formula 20 ll ll )2P o c 0- -c1 0 HC Cl If H (C H O) P o c o a Cl 25 21. The method of claim 6 in which the compound is of the formula 17. The method of claim 6 in which the compound O HC cl cl is of the formula II ll o.Hccl C i H H I 3O ZHSWZP O C O (0 1L1 0) o c 0 -c1 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Parent No. 3,852,438 Dated December 3, 1974 Inventor(s) Henry Martin and Jozef Drabek I It is certified thar error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Colomn 1, line 7: delete "Ciba Limited" and in' lieu thereof insert Ciba-Geigy AG Signed and sealed this 4th day of March 1975.

(SEAL) Attest: C. MARSHALL DANN RUTH C. MASON Commissioner of Patents and Trademarks Arresting Officer USCOMM'DC BO376-P69 fi UIS. GOVERNMENT PRINTING OFFICE IBIS O-HGI SSI,

FORM PO-IOSO (10-69) 

1. A PESTICIDAL COMPOSITION USEFUL FOR COMBATING PESTS SELECTED FROM THE GROUP CONSISTING OF INSECTS AND ACARINAE COMPRISING (1) A PESTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA
 2. The composition according to claim 1 in which, in the compound, each of R1 and R2 represents methyl or ethyl; and R3 represents phenyl or phenyl substituted by from 1 to 5 substituents selected from the group consisting of halogen, methyl, ethyl, methoxy, ethoxy, methylmercapto, nitro, trifluoromethyl, carbethoxy, carbomethoxy, acetyl or propionyl.
 3. The composition according to claim 2 in which, in the compound Hal represents chlorine; and R3 represents phenyl substituted by one methyl or ethyl group or by from 1 to 5 substituents selected from the group consisting of chlorine, bromine, iodine, cyano, nitro or trifluoromethyl.
 4. A method for combatting pests selected from the group consisting of insects, and acarinae, which comprises applying to said pests a pesticidally effective amount of a compound of the formula
 5. The method according to claim 4 in which, in the compound, each of R1 and R2 represents methyl or ethyl; and R3 represents phenyl or phenyl substituted by from 1 to 5 substituents selected from the group consisting of halogen, methyl, ethyl, methoxy, ethoxy, ethylmercapto, nitro, trifluoromethyl, carbethoxy, carbomethoxy, acetyl or propionyl.
 6. The method according to claim 5 in which, in the compound Hal represents chlorine; and R3 represents phenyl substituted by one methyl or ethyl group or by from 1 to 5 substituents selected from the group consisting of chlorine, bromine, iodine, cyano, nitro or trifluoromethyl.
 7. The method of claim 6 in which the compound is of the formula
 8. The method of claim 6 in which the compound is of the formula
 9. The method of claim 6 in which the compound is of the formula
 10. The method of claim 6 in which the compound is of the formula
 11. The method of claim 6 in which the compound is of the formula
 12. The method of claim 6 in which the compound is of the formula
 13. The method of claim 6 in which the compound is of the formula
 14. The method of claim 6 in which the compound is of the formula
 15. The method of claim 6 in which the compound is of the formula
 16. The method of claim 6 in which the compound is of the formula
 17. The method of claim 6 in which the compound is of the formula
 18. The method of claim 5 in which the compound is of the formula
 19. The method of claim 5 in which the compound is of the formula
 20. The method of claim 6 in which the compound is of the formula
 21. The method of claim 6 in which the compound is of the formula 